Process and catalyst for production of olefin polymers



United States Patent 9 PRGCES-S AND ATALYST FOR PRODUCTION OF @iEFiN POLYMERS Gene Nowiin, Glen Burnie, Md., and Harold D. Lyons,

Bartlesvilie, (Elihu, assignors to Phillips Petroleum Company, a corporation of Delaware No Drawing. Application December 16, 1955 Serial No. 553,435

13 'iliaims. (Cl. 260-943) This invention relates to the polymerization of olefins. In one aspect, this invention relates to an improved method for polymerizing olefins and to a novel catalyst therefor.

Reactions for polymerizing olefins are well known in the art and are generally carried out in the presence of catalysts. One class of catalysts which has been used in the polymerization of monoolefins, particularly ethylene, is organometal compounds, for example triethylalumimum, and the polymers which have been obtained in accordance with this method are generally liquid or low molecular Weight solid polymers. Frequently, the polymers obtained are dimers or trimers of the olefin charged. However, it is often desirable to produce higher molecular weight polymers which have desirable properties of heat stability and can be molded into vessels, pipes and tubing. Such uses cannot be made of the lower molecular weight polymers, for example, a polymer having a molecular weight of about 1000, since a polymer of this molecular weight is a wax-like material.

It is an object of this invention, therefore, to provide an improved process for the production of high molecular weight olefin polymers.

A further object is to provide a novel catalyst for use in the production of olefin polymers.

A still further object is to produce high molecular weight solid polymers of olefins, such as ethylene.

Other and further objects and advantages of this invention will become apparent to those skilled in the art upon consideration of the accompanying disclosure.

It has now been discovered that an unexpected improvement in the production of high molecular Weight polymer is obtained when an olefin, such as ethylene, is polymerized in the presence of a catalyst composition comprising (1) a metal halide selected from the group consisting of triand tetrahalides of titanium, zirconium, hafnium and germanium, (2) an organo phosphoruscontaining compound corresponding to the formula R P,

wherein R is selected from the group consisting of a saturated acyclic hydrocarbon radical, a saturated cyclic hydrocarbon radical, an aromatic hydrocarbon radical and combinations of these radicals, and (3) at least one component selected from the following: (a) an organometal halide corresponding to the formula R MX,,, wherein R is a saturated acyclic hydrocarbon radical, a saturated cyclic hydrocarbon radical, an aromatic hydrocarbon radical, or combinations of these radicals as indicated above, wherein M is a metal selected from the group consisting of aluminum, gallium, indium, thallium, and beryllium and wherein X is a halogen, and wherein m and n are integers, the sum of m and n being equal to the valence of the metal; (b) a mixture of an organic halide and at least one metal selected from the group consisting of sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, zinc, cadmium, mercury, aluminum, gallium, indium and thallium; and (c) a complex hydride corresponding to the formula MM"H wherein M is an alkali metal, M" s a metal selected 4 "ice from the group consisting of aluminum, gallium, indium and thallium, and x is equal to the sum of the valences of the two metals.

The improvement obtained when polymerizing an olefin in the presence of our novel catalyst is, firstly, that polymers of much higher molecular Weight possessing very high impact strength and other desirable characteristics can 'be obtained than is true when certain of the prior art catalysts have been employed, and secondly, the polymerization reaction, particularly for ethylene, can be initiated and carried out at considerably lower temperatures and pressures than are necessary when employing the catalysts and the processes of the prior art.

The metal halide component of our catalyst system com-prises the triand tetrahalides of the metals titanium. zirconium, hafnium and germanium. The triand tetrachlorides, triand tetrafluorides, triand tetrabromides, and triand tetraiodides of the aforementioned metals can be used in the catalyst system of this invention, either individually or as a mixture of two or more of the metal halides. Examples of metal halides which can be used include titanium tetrachloride, titanium tetrabromide, titanium trichloride, titanium tribromide, titanium trifluoride, zirconium tetrachloride, zirconium tetrabromide, germanium tetrachloride, germanium tetrabromide, and the like.

In admixture with one or more of the metal halides described above, our novel catalyst comprises an organs phosphorus-containing compound corresponding to the formula R P wherein R is a saturated acyclic hydro carbon radical, a saturated cyclic hydrocarbon radical, an aromatic hydrocarbon radical, or combinations of these radicals. Each of the aforementioned hydrocarbon radicals may contain up to about 20 carbon atoms, preferably from 1 to 10, inclusive, carbon atoms. Mixtures of any two or more of these phosphorus containing compounds can be employed in the practice of our invention. Examples of these compounds which can be used include triphenylphosphine, trimethylphosphine, triisopropylphosphine, tri-tert-butylphosphine, tri-tert-dodecylphosphine, trieicosylphosphine, tri-p-tolylphosphine, tricyclohexylphosphine and the like.

In admixture with at least one of the metal halides and at least one of the phosphorus-containing compounds as set forth above, our catalyst comprises at least one organometal halide corresponding to the formula R M X wherein R is a saturated acyclic hydrocarbon radical, a saturated cyclic hydrocarbon radical, an aromatic hydrocarbon radical, or combinations of these radicals, wherein M is a metal selected from the group consisting of aluminum, gallium, indium, thallium and beryllium, and wherein X is a halogen. The m and n are integers and the sum of m and n is equal to the valence of the metal M. X can be any of the halogens, including chlorine, bromine, iodine and fluorine. The saturated acyclic hydrocarbon radicals, saturated cyclic hydrocarbon radicals, and aromatic hydrocarbon radicals which can be substituted for R in the formula include hydrocarbon radicals aluminum chloride, can be used in our catalyst composition. Specific examples of other organometal halides which are useful in the catalyst composition of this invention are the following: CH AlCl (CH AlCl, C2H5A1C12, (C2H5)2A1Cl, (C2H5)2A1BT, (C4H9)2A},BI', CgHy AlIg, (C3H7)2GaF, (C H11)zGacl (CydOheXaH e derivative), Q H;,)GaBr (benzene derivative),

(benzene derivative), C H lnF (C6H11)II1B1'2 (cyclohexane derivative), C H Bel, CH BeBr, 3-methylcyclohexylaluminum dichloride, 2-cyclohexylethylgallium dichloride, p-tolylberyllium iodide, di-(3-phenyl-l-methylpropyl)indium fluoride, 2-(3-isopropylcyclohexyl)ethylthallium dibromide, and the like.

Alternatively, or in addition to the R MX compounds set forth above, our catalyst comprises a mixture of one or more of the metal halides and one or more of the phosphorus-containing compounds described above and a mixture of an organic halide and a free or elemental metal. These organic halides include chloro-, bromo-, iodoand fiuoro-substituted organic halides, and can be mono-, di-, tri-, or tetra-substituted organic halides. Within the broad class of organic halides which is a component of our novel catalyst composition, the class of halides defined as monohalogen-substituted hydrocarbons having a maximum carbon chain length of not greater than 8 carbon atoms is preferred since they are more easily handled in a commercial operation and are active to initiate the polymerization of olefins in the catalyst composition of this invention. Still more desirably, the organic halide which is used in the catalyst is a lower alkyl monohalide having a maximum carbon chain length of not greater than 8 carbon atoms. Examples of these organic halides which can be used in the catalyst are ethyl bromide, propyl chloride, butyl iodide and pentyl fluoride. Other examples are 1,2-dibromoethane, 1,3-dibromopropane,

chloride, 1,4-dichlorobenzene, 1-bromodecane, l-chlorododecane, 2-chlorooctane, 2-chloro-4-methyloctane, cyclopentyl chloride, l-chloro-3-phenylpropane, l-bromo- 3-phenylhexane, cyclohexyl chloride and phenyl chloride. Also alkenyl halides, such as allyl bromide, and alkynyl halides, such as propargyl chloride, can be used. The metals which are employed in admixture with an organic halide include one or more of sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, zinc, cadmium, mercury, aluminum, gallium, indium, and thallium. The metals are usually used in the form of shavings, turnings or finely divided powder. Various mixtures or combinations of the above-mentioned organic halides and metals can be employed in the catalyst composition of this invention.

Alternatively, or in addition to the R MX compounds and/ or the mixture of an organic halide and a free metal set forth above, our catalyst comprises one or more of the metal halides and one or more of the phosphoruscontaining compounds described above and a complex hydride corresponding to the formula M'MH,, wherein M is an alkali metal, including sodium, potassium, lithium, rubidium and cesium, M" is one of the metals aluminum, gallium. indium or thallium, and x is equal to the sum of the valences of the two metals. Examples of such complex hydrides are lithium aluminum hydride,

. potassium aluminum hydride, sodium aluminum hydride,

cesium aluminum hydride, sodium gallium hydride, lithium, thallium hydride, lithium indium hydride, lithium gallium hydride, rubidium aluminum hydride and the like. The preferred member of this class of compounds is lithium aluminum hydride.

Among the catalyst compositions falling Within the scope of this disclosure which are preferred because their use to catalyze the polymerization of olefins provides relatively high molecular weight polymers and/or permits the use of relatively low reaction temperatures and pressures are the following: a mixture of titanium tetrachloride and triphenylphosphine with an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride; a mixture of titanium trichloride and triphenylphosphine with an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride; a mixture of titanium tetrachloride, tributylphosphine and lithium aluminum hydride; a mixture of zirconium tetrachloride and triphenylphosphine with an approximately equimolar mixture of ethylaluminum dichloride and diethylalumiuum chloride; and a mixture of zirconium tetrachloride and tributylphosphine with an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride.

The amount of the catalyst composition of this invention which is used in the polymerization of olefins can vary over a wide range. Relatively small amounts of the catalyst provide the desired activating effect when the polymerization reaction is carried out as a batch process with continuous addition of the olefin as the poly merization reaction occurs. As much as 50 to 2000 grams of polymer can be obtained per gram of the catalyst composition utilized in the reaction. When a continuous flow system is employed, the concentration of the total catalyst composition is usually in the range from 0.01 weight percent to 1.0 weight percent, or higher.

The ratio of the amounts of organo phosphorus-containing compound to metal halide will generally be in the range of 0.05 to 50, preferably 0.2 to 3, mols of phosphorus-containing compound per mol of metal halide. The ratio of the amounts of organometal halide to metal halide will usually be in the range of 0.05 to 50, preferably 0.2 to 3 mols of organornetal halide per mol of metal halide. The ratio of the amounts of organic halide, metal and metal halide will be in the range of 0.02 to 50 mols of the organic halide per mol of the metal halide and from 0.02 to 50 mols of the metal per mol of the metal halide. A preferred ratio is from 0.2 to 3 mols of organic halide per mol of metal halide andfrom 0.2 to 3 mols of metal per mol of the metal halide. The ratio of the amounts of the complex hydride to metal halide will generally be in the range of 0.05 to 50, preferably 0.2 to 3 mols, of complex hydride per mol of metal halide.

The materials which are polymerized in accordance with this invention can be defined broadly as polymerizable hydrocarbons. Preferably, the polymerizable hydrocarbons are olefins conaining a CH =C radical. The preferred class of polymerizable hydrocarbons used is aliphatic l-olefins having up to and including 8 carbon atoms per molecule. Specifically, the normal l-olefin, ethylene, has been found to polymerize to a polymer thereof upon being contacted with the catalyst composition of this invention at lower temperatures and pressures than have been used in the processes of the prior art mentioned above. Examples of other polymerizable hydrocarbons which can be used in the process of this invention are propylene, l-butene, l-hexene and l-octene. Branched chain olefins can also be used such as isobutylene. Also, 1,1-dialkyl substituted and 1,2-dialkylsubstituted ethylenes can be used, such as butene-Z, pentane-2, hexene-2, heptene-3, Z-methylbutene-l, Z-methylhexene-l, Z-ethylheptene-l, and the like. Examples of the diand polyolefins in which the double bonds are in non-conjugated positions and which can be used in accordance with this invention are 1,5-hexadiene, 1,4-pentadiene and 1,4,7-octatriene. Cyclic olefins can also be used, such as clyclohexene. Mixtures of the foregoing polymerizable hydrocarbons can be polymerized to a solid polymer in the presence of our novel catalyst as, for example, by copolymerizing ethylene and propylene, ethylene and l-butene, propylene and l-butene, or propylene and a pentene. Also, aryl olefins, e. g., styrene and alkyl-substituted styrenes can be polymerized to a solid polymer in the process of this invention. This invention is also applicable to the polymerization of a monomeric material comprising conjugated clienes containing from 4 to 8 or more carbon atoms. Examples of conjugated dienes which can be used include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 2-methoxybutadiene, Z-phenylbutadiene, and the like. It is also within the scope of the invention to polymerize such conjugated dienes either alone or in admixture with each other and/ or with one or more other compounds containing an active CH =C group which are copolymerizable therewith. Examples of such compounds are listed hereinabove. Examples of other compounds containing an active CH =C group include styrene, acrylonitrile, methyl acrylate, methyl methacrylate, vinyl chloride, 2- methyl-S-vinylpyridine, 2-vinylpyridine, and the like.

One of the important advantages obtained in the polymerization of olefins in the presence of our novel catalyst is that lower temperatures and pressures can be used than in certain of the prior art processes. The temperature can be varied over a rather broad range, however, such as from 250 F. and below to 500 F. and above. The preferred temperature range is from 50 to 300 F. Although pressures ranging from atmospheric and below up to 30,000 p. s. i. g. or higher can be employed, a pressure from atmospheric to 1000 p. s. i. g. is usually preferred with a pressure in the range of 100 to 700 p. s. i. g. being even more desirable.

In this connection, it is noted that it is preferred to carry out the reaction in the presence of an inert, organic diluent, preferably a hydrocarbon, with a pressure sufficient to maintain the diluent in the liquid phase, giving rise to a so-called mixed-phase system. However, the polymerization process of this invention proceeds in the gaseous phase without a diluent. The preferred pressure range set forth above has been found to produce solid polymers of olefins in excellent yields.

Suitable diluents for use in the polymerization process are parafiins, cycloparaflins and/or aromatic hydrocarbons which are relatively inert, non-deleterious and liquid under the conditions of the process. The lower molecular weight alkanes, such as propane, butane, and pentane, are particularly useful when carrying out the process at low temperatures. However, the higher molecular weight paraffins and cy'cloparaffins, such as isoctane, cyclohexane and methylcyclohexane and the aromatic diluents, such as benzene, toluene, and the like, can also be used, particularly when operating at higher temperatures. Halogenated hydrocarbons, such as halogenated aromatics, halogenated parafiins and halogenated cycloparaifins, are also useful as diluents. Mixtures of any two or more of the above-listed diiuents can be employed as well in the process of this invention.

The process of this invention can be carried out as a batch process by pressuring the olefin into a reactor containing the catalyst and diluent, if the latter is used. Also, the process can be carried out continuously by maintaining the above-described concentrations of reactants in the reactor for a suitable residence time. The residence time used in a continuous process can vary widely, since it depends to a great extent upon the temperature at which the process is carried out. The residence time also varies with the specific olefin that is polymerized. However, the residence time for the polymerization of aliphatic monoolefins, within the preferred temperature range of 50 to 300 F., falls within the range of one second to an hour or more. In the batch process, the time for the reaction can vary widely also, such as up to 24 hours or more.

In carrying out the polymerization reaction of this invention, the catalyst components can be charged to the reaction vessel in any desired order. In one preferred method when operating batchwise, the metal halide and the organo phosphorus-containing compound are heated together and then charged to the reactor. Thereafter, the organornetal halide, the organic halide and metal and/or the complex hydride are introduced into the reactor. In another method of operation, all three of the catalyst components are charged simultaneolsly to the reaction vessel. This latter method is especially applicable when carrying out the process in a continuous manner.

It has been found that various materials in some instances may have a tendency to inactivate the catalyst compositions of this invention. These materials include carbon dioxide, oxygen and water. Therefore, it is usually desirable to free the polymerizable hydrocarbon from these materials, as well as from other materials which may tend to inactivate the catalyst before contacting the hydrocarbon with the catalyst. Any of the known means for removing such contaminants can be employed. When a diluent is used in the process, this material should generally be free of contaminants, such as water, oxygen, and the like. It is desirable, also, that air and moisture be removed from the reaction vessel before the reaction is carried out. However, in some cases small amounts of catalyst inactivating materials, such as oxygen or water, can be tolerated in the reaction mixture while still obtaining reasonably good polymerization rates. It is to be understood that the amount of such materials present in the reaction mixture shall not be sufiicient to completely inactivate the catalyst.

At the completion of the polymerization reaction, when a batch process is used, the reactor is cooled to about room temperature, any excess olefin is vented and the contents of the reactor, including the solid polymer swollen with diluent, is then treated to inactivate the catalyst, as by washing with an alcohol. The alcoholwashing step ispreferably carried out in a comminution zone, such as a Waring Blendor, so that a finely-divided polymer is thereby provided. The polymer is then separated from the alcohol and diluent by decantation or filtration and then the polymer is dried. When the process of the invention is carried out continuously, the total effluent from the reactor, including polymer, diluent and catalyst system is pumped from the reactor as a slurry to a catalyst-inactivating zone where the reactor effluent is cooled and contacted with a suitable catalystinactivating material, such as an alcohol, to precipitate the polymer. As in thebatch process, it is desirable that the alcohol-treatment step be. carried out in a comminuation zone so that a finely divided polymer is thereby produced. The diluent and alcohol are then separated from the polymer, for example, by filtration and the polymer is then dried. The diluent and alcohol can be separated, for example by fractional distillation, and reused in the process.

A more comprehensive understanding of the invention may be obtained by referring to the following illustrative example which is not intended, however, to be unduly limitative.

EXAMPLE I Ethylene was polymerized in a 1200 cubic centimeter stainless steel rocking autoclave in the presence of a catalyst consisting of a mixture of 3.55 grams of titanium tetrachloride and 4 grams of a mixture of diethylalumimnn chloride and ethylaluminum dichloride. The mixture of diethylalurninum chloride and ethylaluminum dichloride was prepared in accordance with the procedure described hereinafter. The catalyst was dissolved in 500 cubic centimeters of benzene (dried over sodium) and charged to the autoclave while maintaining the autoclave under a nitrogen atmosphere. The ethylene was passed through a purification system to remove oxygen, carbon dioxide and water vapor prior to entering the autoclave. The

' purification system comprised a pyrogallol solution, a

sodium hydroxide solution and drying agents. The ethylene was charged to the autoclave while maintaining the catalyst and diluent at atmospheric pressure. The polymerization of the ethylene was immediately initiated, and as the addition of ethylene continued the temperature of the reaction mixture increased rapidly to F. The ethylene was passed into the autoclave as rapidly as the limitations of the purification system would permit. Maximum pressure reached in the autoclave was 300 p. 's. i. g. At the end of a 15 minute reaction period, the bomb was opened, and a polymer of ethylene was present as a suspension in the benzene solutionv One hundred cubic centimeters of butyl alcohol was added to the autoclave to inactivate the catalyst. The solid polymer was filtered from the benzene-alcohol mixture and then washed with isopropyl alcohol. After filtering the polymer from the isopropyl alcohol, it was dried overnight in a vacuum oven at about 140 F. About 100 grams of polyethylene was obtained.

The properties of a sample of the ethylene polymer produced as described above are presented below in Table I.

Table I Molecular weight (based on melt index) 9,025. Density, grams/cc, at room temperature 0.941. Flexibility Quite brittle.

Impact strength (falling ball method) Broke at 6".

Melt index 445.0.

Melting point, F 242:2.

Inherent viscosity 0.451.

Color Light tau.

EXAMPLE ll Ethylene was polymerized in a 2700 cubic centimeter stainless steel reactor in the presence of a catalyst consisting of 3.5 grams of titanium tetrachloride, ten grams of triphenylphosphine and 4 cubic centimeters of a mixture of diethylaluminurn chloride and ethylaluminum dichloride. This latter mixture was prepared according to the procedure described hereinbelow. The reactor was llushed with purified nitrogen prior to and during the charging procedure to prevent contact of the catalyst with air or moisture. The 3.5 grams of titanium tetrachloride was dissolved in 500 cubic centimeters of cyclohexane (distilled from sodium) and charged to the reactor under pressure of purified nitrogen. The 10 grams of triphenylphosphine was then charged to the reactor after which 4 cubic centimeters of the mixture of diethylaluminum chloride and ethylalurninum dichloride was charged. The ethylene feed was passed through a purification system to remove oxygen, carbon dioxide, and water vapor prior to entering the reactor. The purification system cornprises a pyrogallol solution, a sodium hydroxide solution and drying agents.

Ethylene was pressured into the reactor containing catalyst until a pressure of 300 p. s. i. g. at 95 F. was

reached. Heat was applied to the reactor, and when the polymerization started, the heat source wa removed and the polymerization allowed to continue for about 130 minutes. During this period, the temperature rose to 300 F. The reactor was then cooled and opened, and a very tough polymer was recovered. The product was comminuted in a Waring Blender for about 30 minutes, filtered, and dried overnight in a vacuum oven at 75 C. Approximately 42 grams of white polymer was obtained. The properties of a sample of this polymer are presented below in Table II.

T able II Molecular weight l00,000. Density, grams/cc, at room temperature 0.972. Flexibility Good. Impact strength (falling ball method) r 72". Moldability Good. Melt index Did not extrude. Melting point, F 254:2. Inherent viscosity (in tetralin) a- Insoluble. Color Yellowish white.

The mixture of diethylaluminum and ethylaluminum dichloride was prepared by placing 150 grams of aluminum shavings in a flash fitted with a reflux condenser and heated to about 70 C. A trace of iodine was added to the flash to act as a catalyst, and ethyl chloride was charged to the flask in liquid phase. The temperature of the reaction mixture was maintained in the range of to C. during the addition of ethyl chloride, and the reaction mixture was maintained under a nitrogen atmosphere. When substantially all of the aluminum shavings had reacted with the ethyl chloride, the liquid product was removed from the flask and fractionally distilled at 4.5 millimeters of mercury pressure in a packed distillation column. The distillate, boiling at 72 to 74 C. at 4.5 millimeters of mercury pressure, was used in the catalyst compositions of Examples I and II in the amounts specified hereinabove. This fraction boiling at 72 to 74 C. was analyzed and found to contain 47.4 weight percent chlorine. The theoretical chlorine content for an equimolar mixture of diethylaluminum chloride and ethylaluminum dichloride is 43 weight percent.

From a consideration of the data shown in Tables I and II, it is seen that the addition of triphenylphosphine to the catalyst composition consisting of titanium tetrachloride and a mixture of diethylaluminum chloride and ethylaluminum dichloride resulted in an ethylene polymer having a molecular weight in excess of 100,000 and possessing greatly increased impact strength.

The polymers produced in accordance with this invention have utility in applications where solid plastics are used. They can be used to impregnate paper and tabrics, and they can be molded to form articles of any desired shape, such as bottles and other containers for liquids. Furthermore, they can be formed into pipe by extrusion.

As will be evident to those skilled in the art, many variations and modifications can be practiced Within the scope of the disclosure and claims of this invention. The invention resides in an improved polymerization process for olefins as described herein comprising the use of a novel catalyst composition and the catalyst so produced, said catalyst composition comprising (1) a metal halide selected from the group consisting of triand tetrahalides of titanium, zirconium, hafnium and germanium, (2) an organo phosphorus-containing compound corresponding to the formula R 1, wherein R is selected from the group consisting of a saturated acyclic hydrocarbon radical, a saturated cyclic hydrocarbon radical, an aromatic hydrocarbon radical and combinations of these radicals, and (3) at least one component selected from the following: (a) an 'organometal corresponding to the formula R MX wherein R is as defined hereinabove, M is a metal selected from the group consisting of aluminum, gallium, indium, thallium and beryllium, and X is a halogen, and wherein m and n are integers, the sum of m and n being equal to the valence of the metal M; (b) a mixture of an organic halide and at least one metal selected from the group consisting of sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, zinc, cadmium, mercury, aluminum, gallium, indium and thallium; and (c) a complex hydride corresponding to the formula M'M"H wherein M is an alkali metal, M" is a metal selected from the group consisting of aluminum, indium, gallium and thallium, and x is equal to the sum of the valences of the two metals M and M".

We claim:

1. A method for polymerizing a polymerizable hydrocarbon containing ethylenic unsaturation which comprises contacting said hydrocarbon with a catalyst comprising (1) a metal halide selected from the group consisting of triand tetrahalides of titanium, zirconium, hafnium and germanium, (2) an organo phosphorus-containing compound corresponding to the formula RgP, wherein R is selected from the group consisting of a saturated acyclic hydrocarbon radical, a saturated cyclic hydrocarbon radical, an aromatic hydrocarbon radical and combinations of these radicals, and (3) at least one component selected from the following: (a) an organometal corresponding to the formula R MX wherein R is as defined hereinabove, M is a metal selected from the group consisting of aluminum, gallium, indium, thallium and beryllium, and X is a halogen, and wherein m and n are integers, the sum of m and n being equal to' the valence of the metal M; (b) a mixture of an organic halide and at least one metal selected from the group consisting of sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, Zinc, cadmium, mercury, aluminum, gallium, indium and thallium; and (c) a complex hydride corresponding to the formula M'M"H wherein M is an alkali metal, M" is a metal selected from the group consisting of aluminum, gallium, indium and thallium, and x is equal to the sum of the valences of metals M and M".

2. A method in accordance with claim 1 wherein said polymerizable hydrocarbon is an aliphatic l-olefin having up to and including 8 carbon atoms per molecule.

3. A method in accordance with claim 1 wherein said polymerizable hydrocarbon is ethylene and said catalyst consists essentially of a mixture of titanium tetrachloride, triphenylphosphine, and an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride.

4. A method in accordance with claim 1 wherein said polymerizable hydrocarbon is ethylene and said catalyst consists essentially of a mixture of titanium trichloride, triphenylphosphine, and an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminurn chloride.

5. A method in accordance with claim 1 wherein said polymerizable hydrocarbon is ethylene and said catalyst consists essentially of a mixture of titanium tetrachloride, tributylphosphine, and lithium aluminum hydride.

6. A method in accordance with claim 1 wherein said polymerizable hydrocarbon is ethylene and said catalyst consists essentially of a mixture of zirconium tetrachloride, triphenylphosphine, and an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride.

7. A method in accordance with claim 1 wherein said polymerizable hydrocarbon is ethylene and said catalyst consists essentially of a mixture of zirconium tetrachloride, tributylphosphine, and an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride.

8. A polymer produced in accordance with the method of claim 1.

9. A method for producing a solid polymer of an aliphatic l-olefin having up to and including 8 carbon atoms per molecule which comprises contacting said olefin with a catalyst comprising (1) a metal halide selected from the group consisting of triand tetrahalides of titanium, zirconium, hafnium and germanium, (2) an organo phosphorus-containing compound corresponding to the formula R P, wherein R is selected from the group consisting of a saturated acyclic hydrocarbon radical, a saturated cyclic hydrocarbon radical, an aromatic hydrocarbon radical and combinations of these radicals, and (3) at least one component selected from the following: (a) an organometal corresponding to the formula R MX wherein R is as defined hereinabove, M is a metal selected from the group consisting of aluminum, gallium, indium, thallium and beryllium, and X is a halogen, and wherein m and n are integers, the sum of m and n being equal to the valence of the metal M; (b) a mixture of an organic halide and at least one metal selected from the group consisting of sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, zinc, cadmium, mercury, aluminum, gallium, indium and thallium; and (c) a complex hydride corresponding to the formula M'M"H wherein M' is an alkali metal, M" is a metal selected from the group consisting of aluminum, gallium, indium and thallium, and x is equal to the sum of the valences of metals M and M"; at a temperature in the range of 10 -250 F. to 500 F., in the presence of a hydrocarbon diluent, inert and liquid under conditions of the method, at a pressure sufiicient to maintain said diluent in liquid phase, and recovering the solid polymer so produced.

10. A method in accordance with claim 9 wherein the ratio of the amounts of the components of said catalyst are in the following ranges: from 0.05 to 50 mols of said organo phosphorus-containing compound per mol of said metal halide; from 0.05 to 50 mols of said organometal halide per mol of said metal halide; from 0.02 to 50 mols of said organic halide per mol of said metal halide and from 0.02 to 50 mols of said metal per mol of said metal halide; and from 0.05 to 50 mols of said complex hydride per mol of said metal halide.

11. A method in accordance with claim 9 wherein the ratio of the amounts of the components of said catalyst are in the following ranges: from 0.2 to 3 mols of said organo phosphorus-containing compound per mol of said metal halide; from 0.2 to 3 mols of said organometal halide per mol of said metal halide; from 0.2 to 3 mols of said organic halide per mol of said metal halide and from 0.2 to 3 mols of said metal per mol of said metal halide; and from 0.2 to 3.0 mols of said complex hydride per mol of said metal halide.

12. A method for polymerizing ethylene which comprises contacting ethylene with a catalyst consisting essentially of a mixture of titanium tetrachloride, triphenylphosphine, and an approximately equimolar mixture of diethylaluminum chloride and ethylaluminum dichloride, in the presence of a hydrocarbon diluent, inert and liquid under conditions of the method, at a temperature in the range of 50 to 300. F., and a pressure in the range of to 700 p. s. i. g.

13. A catalyst composition comprising (1) a metal halide selected from the group consisting of triand tetrahalides of titanium, zirconium, hafnium and germanium, (2) an organo phosphorus-containing compound corresponding to the formula R P, wherein R is selected from the group consisting of a saturated acyclic hydrocarbon radical, a saturated cyclic hydrocarbon radical, an aromatic hydrocarbon radical and combinations of these radicals, and (3) at least one component selected from the following: (a) an organometal corresponding to the formula R MX wherein R is as defined hereinabove, M is a metal selected from the group consisting of aluminum, gallium, indium, thallium and beryllium, and X is a halogen, and wherein m and n are integers, the sum of m and n being equal to the valence of the metal M; (b) a mixture of an organic halide and at least one metal selected from the group consisting of sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, zinc, cadmium, mercury, aluminum, gallium, indium and thallium; and (c) a complex hydride corresponding to the formula M'MH wherein M is an alkali metal, M" is a metal selected from the group consisting of aluminum, gallium, indium and thallium, and x is equal to the sum of the valences of metals M and M.

14. A catalyst composition consisting essentially of a mixture of titanium tetrachloride, triphenylphosphine, and an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride.

15. A catalyst composition consisting essentially of a mixture of titanium trichloride, triphenylphosphine, and an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride.

16. A catalyst composition consisting essentially of titanium tetrachloride, tributylphosphine, and lithium aluminum hydride.

17. A catalyst composition consisting essentially of a mixture of zirconium tetrachloride, triphenylphosphine, and an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride.

18. A catalyst composition consisting essentially of a mixture of zirconium tetrachloride, tributylphosphine, and

11 an approximately equimolar mixture of ethylaluminum 2,712,189 trichloride and diethylaluminum chloride.

References Cited in the file 0f this patent UNITED STATES PATENTS 02,5 533,362

2,520,601 Lee Aug. 29, 1950 12 Anderson et a1 Oct. 18, 1955 FOREIGN PATENTS Canada May 18, 1954 Belgium May 16, 1955 

1. A METHOD FOR POLYMERIZING A POLYMERIZABLE HYDROCARBON CONTAINING ETHYLENIC UNSATURATION WHICH COMPRISES CONTACTING SAID HYDROCARBON WITH A CATALYST COMPRISING (1) A METAL HALIDE SELECTED FROM THE GROUP CONSISTING OF TRI- AND TETRAHALIDES OF TITANIUM, ZIRCONIUM, HAFNIUM AND GERMANIUM, (2) AN ARGANO PHOSPHORUS-CONTAINING COMPOUND CORRESPONDING TO THE FORMULA R3P, WHEREIN R IS SELECTED FROM THE GROUP CONSISTING OF A SATURATED ACYCLIC HYDROCARBON RADICAL, A SATURATED CYCLIC HYDROCARBON RADICAL, AN AROMATIC HYDROCARBON RADICAL AND COMBINATIONS OF THE RADICALS, AND (3) AT LEAST ONE COMPONENT SELECTED FROM THE FOLLOWING: (A) AN ORGANOMETAL CORRESPONDING TO THE FORMULA RMMXN WHEREIN R IS AS DEFINED HEREINABOVE, M IS A METAL SELECTED FROM THE GROUP CONSISTING OF ALUMINUM, GALLIUM, INDIUM, THALLIUM AND BERYLLIUM, AND X IS A HALOGEN, AND WHEREIN M AND N ARE INTEGERS, THE SUM OF M AND N BEING EQUAL TO THE VALENCE OF THE METAL M; (B) A MIXTURE OF AN ORGANIC HALIDE AND AT LEAST ONE METAL SELECTED FROM THE GROUP CONSISTING OF SODIUM, POTASSIUM, LITHIUM, RUBIDIUM, CESIUM, BERYLLIUM, MAGNESIUM, ZINC, CADMIUM, MERCURY, ALUMINIUM, GALLIUM, INDIUM AND THALLIUM; AND (C) A COMPLEX HYDRIDE CORRESPONDING TO THE FORMULA M''M"H$, WHEREIN M'' IS AN ALKALI METAL, M" IS A METAL SELECTED FROM THE GROUP CONSISTING OF ALUMINUM, GALLIUM, INDIUM AND THALLIUM, AND X IS EQUAL TO THE SUM OF THE VALENCES OF METALS M'' AND M". 